Germicidal detergent



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UNITED STATES PATENT OFFICE GERMICIDAL DETERGENT Milward Bayliss,Hurloek, Md., and John L.

Wilson, St. Paul, and Erling J. Ordal, Minneapolis, Minn., assignors toEconomics Labora'tory Inc., St. Paul, Minn., a corporation of DelawareNo Drawing. Application May 10, 1935,

.Serial No. 20,766

3 Claims.

This invention relates to improvements in germicidal detergentcompositions and includes such compositions in a concentrated or drystate, such as a dry powder, as well as germicidal solutions of suchcompositions.

The new compositions are valuable for use in homes, hotels, restaurants,hospitals and institutions, as well as in the beverage and dairyindustries, where a germicidal action as well as a detergent action isdesired.

The new germicidal detergent compositions are in general admixtures ofalkalies or buffer salts and wetting agents of the character hereafterreferred to, in such proportions that when, for example, a solution ismade of the composition containing from to 3% of the composition thesolution will have a high pH value, in excess of about'11.5.

The buffer salts which are used in the new composition are alkalinesalts or alkalies, such, 'as'carbo'nates, phosphates or silicates, etc.,used in such amounts and proportions as will give to the final solutionthe desired pH value. Among such buffer salts may be mentioned sodiumcarbonate, mono-sodium-phosphate, disodium phosphate, tri-sodiumphosphate, sodium silicates, etc.

In using these buffer salts, in making the new composition, the properpH is obtained by a selection of the buffer salts employed which may, insome cases, be a single salt or salts of the same acid, or salts ofdifferent acids, etc. For example, the proper pH may be obtained by theuse of a mixture of various phosphates and carbonates, or variousphosphates and silicates, or carbonates and silicates, or by mixtures ofphosphates, carbonates and silicates; as well as by mixtures of variousphosphates alone, or carbonates alone, or silicates alone. Similarly,other salts besides phosphates, carbonates and silicates may be used toobtain the proper pH.

The wetting agents which are used, together with the alkaline salts, inmaking the new compositions, are in general wetting agents of acharacter which are superior to and distinguished from ordinary soap.Among the important wetting agents which are employed in accordance withthe present invention, are sulfonated products such as sulfonatedhydrocarbons or sulfonated higher alcohols and sulfonated oils which arefree from a carboxyl (free or neutralized) group or which have acarboxyl group blanked or made ineffective. Certain phenolic oralcoholic Wetting agents are also included.

The sulfonated higher fatty alcohols have re- I cently been introducedin commerce as wetting agents and these are well adapted for use in thenew composition of the present invention. The

higher alcohols are obtainable by catalytic reduction, under properconditions, from the fatty acids'of natural fats and their esters. Whensulfonated with concentrated sulfuric acid under proper conditions theyyield products known in the trade as fatty alcohol sulfates or halfsulfuric acid esters of the fatty alcohols. While referred to assulfonated fatty alcohols, they are more properly referred to as alkylesters of sulfuric acid having for example the general formulaR.O.SO2.ONa, where R is a straight chain aliphatic radical containing 8or 10 carbon atoms or more. A simpler formula for these sulfonated fattyalcohols is R.SO4Na, representing the'sodium'salts of the alkylsulfates, where R is a long chain aliphatic radical. Among thesesulfonated fatty alcohols may be mentioned sodium lauryl sulfate, sodiumoctadecyl sulfate, and sodium oleyl sulfate. The technical grade ofsulfonated JauryL alcohol ,is known. as sulfonated Lorol and thetechnical grade of sulfonated oleic or oleyl alcohol is known assulfonated Ocencl.

Where the alcohol'sulfonated is an unsaturated alcohol the sulfuric acidmay react by addition at the double bond to form sulfonicor sulfatederivatives as well as by' reaction with the hydroxyl group to form theester. The products may be in part true sulfonic acids or may containtrue sulfonic acids as well as sulfates or suifuric acid esters. Whenchloro-sulfonic acid is used for sulfonating the unsaturated alcoholstrue sulfonic acids are produced and where the al coholic hydroxyl isconverted into a sulfate the sulfonated alcohol may contain both asulfonic and a sulfate group. The sulfonated higher alcohols aremarketed under various trade names, such as Gardinols, BrilliantAvirols, Orvus,Dreft, etc. The sodium oleyl sulfate, for example, is

marketed under the trade name Gardinol CA and' the lauryl sodiumsulfonate is marketed under the trade name Gardinol WA. The higher fattyalcohol sulfonates derived from stearyl and cetyl alcohols are marketedunder the trade names Brilliant- Avirols L142, L144 and L168. Thesevarious sulfonated alcohol products are used in the form of their sodiumsalts. I

The sulfonated higher alcohols, although produced by the sulfonating ofthe alcohols, are in.

sulfonic acid is sold under the trade names Neomerpin, Erkalin andAlkanol SA. The alkylated naphthalene sulfonic or sulfuric acid productsare used in the form of their sodium salts, for example, the sodiumisopropyl naphthalene sulfonate. Other sulfonated hydrocarbons arerepresented by sulfonated abietenes, or suli'onated abietanes, forexample, sodium abietene sulfonate; or the sodium salt of sulfonatedabietanes (hydrogenated abietenes), The naphthalene sulfonic acidcompound may be combined with one of the fatty sulfonic acid compounds,as in Oranit BN Extra. The. sodium salts of naphthalene 'sulfonic acidderivatives are also marketed under the trade name Alkanol. Sodiumtetralin sulfonate is also marketed under the trade name Alkanol S.Sodium tetrahydro naphthalene sulfonate is the active wetting agent inAlkanol PF.

Certain sulfonated wetting agents are made from oleic acid andisethionic acid. The prodnot having the formula CH3 (CH2) 7CH 2 CH CH2)7COOCH2CH2SO3N8.

is sold under the trade name Igepon A. A somewhat different producthaving the formula CHJ(CHI)7CH:CH(CH2)1CONCHZCHZSOSNB I is sold underthe trade name Igepon T. Igepon T in a solvent is sold under the tradename Laven-' sold in the trade as Avirol AH Extra. Sulfonated fatty oilsare sold under the trade names Nopco Castor and Intrasol.

The sodium salt of the sulfuric ester of oleic gclid amide is sold underthe trade name Humeco C.

The various wetting agents are used in the new composition in the formof their sodium salts together with the buffer or alkaline salts in suchproportions that there will be present in the solution made of thecomposition only a small percentage of the wetting agent together withsuch amount of the buffer salt as will give to the solution. a Qgh pHvalue of around 11.5 or higher. While the wetting agents themselves arerelatively inefiective as germicides, the compositions in which they areused together with the alkaline salts are highly eifective, such thatsolutions from the new compositions are excellent detergents and exhibitsufficient germicidal properties so that they can also be used asgermicides. In general the solutions made from the new compositions willcontain .from around to 3% of the composition, although the amount canbe somewhat varied.

The new compositions are advantageously compounded and marketed in theform of'a dry powder containing the wetting agent, where available in adry powdered form, together with'the pulverulent alkaline salt, in theform of an intimate and substantially homogeneous mixture, such that adefinite weight of the powdered composition can be used to give asolution of definite strength and proportions of the differentingredients. Such a dry mixture of the ingredients can be readilyproduced, handled, shipped and stored and a definite amount measured orweighed out for use in producing germicidal detergent solutions.

The particular alkali salt or salts used in the composition for givingit the desired high pH value can be varied and are best defined by thepH value of the resulting solution rather than by attempting to give thevarious combinations of chemicals which will provide the desired high pHvalue.

In testing the solutions of the new composition, we have used thefollowing test: The dry mixture, containing the ingredients of thecomposition, is made into a solution of from A to 3% strength. To 5 cc.of this solution is added cc. of a 24 hour culture of the standard testorganism, Staphylococcus aureus (Insecticide Board strain). Before theculture is added to the test solution, it is brought to the requiredtemperature; the temperature we have used has been 37 C. or in somecases a higher temperature. After the culture has been in the testsolution for five minutes, a 4 mm. loopful is removed and added to atube of molten agar at a temperature of 45 C-. and the mixture is pouredinto a Petri plate. The plates are incubated for 48 hours, at the end ofwhich time a count is made of the colonies appearing on the plate. Thenumber of organisms originally added to thetest solution is in theneighborhood of five hundred millions (500,000,000). If no organisms arekilled, the loopful removed will contain an excess of 10,000 organisms,and therefore the number of colonies appearing on the plates will be, inexcess of 10,000. If some of the organisms are killed, the number ofcolonies appearing on the plates will be less than 10,000. In the datareported in the following examples, the numbers indicate the coloniesappearing on the test plate after 48 hours of incubation. Similar testswere made using Eberthella typhi (Hopkins strain).

As illustrating the action of water alone, sodium lauryl sulfate alone,in various amounts, sodium carbonate, trisodium phosphate, sodiummeta-silicate and sodium sesqui-silicate, the following table gives theresults of tests made as above described, with these various substances,the tests being carried out with Staphylococcus aureus (F. D. A. strain)at a temperature of 37 C. and with a plate count after 5 minutes and 10minutes respectively. The organism employed and the temperature and timeof the test are in accordance with the standards adopted by the FederalFood .and Drug Administration (F. D. A.)

Plate counts Solution tested.

5 min 10 min.

Water alone 10, 000+ 10,000+ 0.01%.sodium lauryl sulfate 10. 000+ 10,000+ 0.1% sodium lauryl suliate 10. 000+ 10. 000+ 1.0% sodium laurylsulfate 10,000+ 10,000+ 2.0% sodium lauryl sulfate 10. 000+ 10.0004- 1%sodium carbonate (NmCOa) (DH=11.4) 10, 000+ 10. 000+ 2% sodium carbonate(NazOOz) (pH=1l.5) 10. 000+ 10. 000+ 1% T. S. P. (trisodium phosphate)(N8zPO4.12HzO) (pH=12.0) 10,000+ 10.000+

o T. S. P. (trisodium phosphate) (N8zP04.12Hz0) (pH=l2.2) 3, 000+ 3,000+2% Metso (sodium metasilicate) (NagSiOafiHzO) (pH=12.6) 1.800 900 1%Metso (sodium metasilicate) (NazSiO;.5H10)(pH=12.3) 10, 000+ 8, 000+ 1%Metso 99 (sodium sesquisilicate (pH=12.6) 2, 000 800 LJLI From thistable it will be seen that the various alkaline salts alone areineffective at this temperature and in these concentrations asgermicides and that the sodium lauryl sulfate is likewise ineifective.However, when sodium lauryl sulfate or.other effective wetting agents,such as those above referred to are used in combination with thealkaline salts, a pronounced germicidal action as wellas detergentaction is obtained. The germicidal action of sodium lauryl sulfate invarious amounts used together with trisodium phosphate and sodiummeta-silicate (Metso) are illustrated by the following table, theorganism used, the temperature, etc., being those above referred to:

5 min. 0 min.

+.0l% sodium lauryl sulfate +.01'5% sodium lauryl sulfate +.02%sodiumlauryl sulfate +.05%'sodium lauryl sulfate 2% 'l. +.l% sodium laurylsulfat 2% 'l. +.5% sodium lauryl sulfate. 1% Metso +01% sodium laurylsulfate 1% Metso +0.05% sodium lauryl sulfate 1% Metso +0.02% sodiumlauryl sulfate 1% Metso +0.015% sodium lauryl sulfate 1% Metso +0.01%sodium lauryl sulfate 2% Metso +01% sodium-lauryl sulfate. 2% Metso+0.05% sodium lauryl sulfate 2% Mctso +0.02% sodium lauryl sulfate 2%Metso +0.0l5% sodium lauryl sulfate. 2% Metso +0.01% sodium laurylsulfate M ooccosmwooococw Plate counts Solution tested 5 min. 10 min.

The results of tests made as above described with compositions made withvarious wetting agents and with sodium meta-silicate or sodiumcarbonate, in accordance with the tests above referred to are given inthe following table:

Plate counts Solution tesferl 5 min. 10 min.

W'ater alone 10, 000+ 10, 000+ 1% Metso (sodium metasilicate)(N8zSiOa.5H:O) (pl2 [=12.3) 10. 000+ 8,000 1% Metso+.1% Erkal1n 125 151% Metso+.2% ErkalilL 0 0 1% Metso+.l% Alkanol B. 200 30 1% Metso+.2%Alkanol B. '5 0 1% Metso+.2% Merpentine 6 0 1% Mctso+.2% Alkanol SA l5 31% Metso+.2% Orvus (sodium lauryl sulfate). 20 0 1% Metso+0.2% sodiumstearyl sulfate 40 0 1% Metso+0.2% Alkanol PF. 40 0 1% Metso+0.2%Laventine KB 125 2 1% Metso+0.2% sodium oleyl sulfate 250 3 1%Metso+0.2% Humcctol C .i 300 5 Another series of tests made withcompositions containingsodium meta-silicate and a fraction of a percentof various wetting agents is indicated by the following table, thetemperature maintained in these tests being 45 C. and the same organismbeing used as in the tests laLJi'ui w ry-g above referred to, the lastthree solutions representing phenol solutions used as control:

Solution tested 5 min. 10 min.

MOOOCOOQOO ooooopcooco From the above examples it will be noted that thesolution tested contained only a small fraction of a percent of thewetting agent and only around 1 or 2% of the total composition, but thesolution was nevertheless effective as a germicide in addition to itsdetergent properties.

,The wetting agents used in the composition impart improved penetratingproperties to the composition, making the composition effective in itsdetergent as well as its germicidal properties.

In general the amounts of wetting agents will be around 0.002% orhigher, the amount to be used 3 in practice depending on the wettingagent used,

on the pH of the solution, on the temperature of the solution, and onthe length of time of contact with and the kind of organisms to bekilled. 1

In general the amount of the wettiiig'ag'fifiwill form only a smallproportion of the dry mixture, where the composition is prepared andmarketed in dry form, the greater part of the composition being made upof the alkaline or buffer salts of such nature and amount as will impartto the solution of the composition the desired high pH value. I

The new compositions are useful for many purposes as in hospitals orinstitutions, where germicidal detergents are important, as well as in45 hotels and restaurants for dish-washing and other purposes, and invarious industries such as the beverage and dairy industries, where itis important, for example, to sterilize the bottles and containers aswell as to wash them.

' In some cases it is advantageous to use a plu-. rality or mixture ofactive wetting agents, instead of only one active wetting agent, in thenew composition. The active wetting agents differ somewhat in theirdetergent or sudsing 55 properties, and it is sometimes advantageous toadd a wetting agent which is less ineffective in the germicidalproperties which it imparts to the composition together with anotheractive wetting agent which is more effective, thereby 0 obtaining abalance in antiseptic and detergent properties by the use of two or moreactive wetting agents which differ somewhat from each other in theirproperties, or one of which, though more effective, is more expensive,and can be 5 advantageously used in smaller amounts together with one ormore other active wetting agents.

It will be understood that, where a mixture or plurality of activewetting agents is used, the alkali salt, or mixture of alkali salts usedto give 7 to the solution the high pH value, can be varied, and a singlesalt, or a mixture of salts, used, in such proportions as will insure inthe resulting solution the desired high pH value.

By the term wetting agents we. mean those Plate counts 5 wetting agentswhich are sulfonated products such as sulfonated hydrocarbons orsulfonatedhigher alcohols, and which are free from carboxyl groups,whether free or neutralized, or which have carboxyl groups blanked ormade ineffective in a suitable manner, as by substituting for thehydrogen of the carboxyl group an alkyl group, or an amido group, orother suitable group and which do not form objectionable precipitateswith calcium and magnesium ions found in hard water, as distinguishedfrom ordinary soaps, which are neutralized carboxylic acids and whichform objectionable precipitates with calcium and magnesium ions presentin hard water.

We claim: e

1. A germicidal detergent composition comprising a sulfonated alcoholwetting agent and alkaline salts in such proportions that an aqueoussolution containing from to 3% of the composition will have a pH valuein excess of about 11.5 and will contain a small fraction of 1% of thesulfonated alcohol.

2. A germicidal detergent composition comprising sodium lauryl sulfateand alkaline salts in such proportion that an aqueous solutioncontaining from /2 to 3% of the composition will contain a smallfraction of 1% of the sodium lauryl sulfate and will have a pH value inexcess of about 11.5.

' 3. A germicidal detergent composition containing a major proportion of'bufier salts and containing a-relatively small proportion of a mixtureof active sulfonated wetting agents, including a sulfonated alcoholwetting agent, said composition being adapted when dissolved in water inamounts ranging from /2 to 3% to form a gel icidal detergentsolution'containing a small if n of 1% of the wetting agents with asufllcient amount of the alkaline salts to give a pH value in excess ofabout 11.5.

